WO1998027604A1 - Hydrogen storage alloys of the ab5 type for use in rechargeable electrochemical cells, and methods of producing them - Google Patents
Hydrogen storage alloys of the ab5 type for use in rechargeable electrochemical cells, and methods of producing them Download PDFInfo
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- WO1998027604A1 WO1998027604A1 PCT/US1997/023271 US9723271W WO9827604A1 WO 1998027604 A1 WO1998027604 A1 WO 1998027604A1 US 9723271 W US9723271 W US 9723271W WO 9827604 A1 WO9827604 A1 WO 9827604A1
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- Prior art keywords
- alloy
- alloying element
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- zirconium
- titanium
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
- H01M4/385—Hydrogen absorbing alloys of the type LaNi5
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/34—Gastight accumulators
- H01M10/345—Gastight metal hydride accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to hydrogen storage alloys for use in rechargeable electrochemical cells.
- Hydrogen storage alloys provide improved 5 performance characteristics such as high energy density, longer charge retention, longer cycle life and low temperature operation, when used in rechargeable electrochemical systems.
- LaNi 5 alloys which have a high hydrogen content and high hydrogen storing capacity has been widely reported.
- lanthanum is an expensive element, and commercial, large-scale utilization of such an alloy is not 5 practical.
- U.S. Patent No. 4,107,405 describes electrode materials based on lanthanum and nickel having a formula close to LaNi 5 in which one of the components is partially substituted by a metal selected from those in groups la, II, III, IV and Va of the Periodic Table of elements, and other than lanthanides, in an atomic proportion which is not zero, being higher than 0.1 percent and lower than 25 percent with respect to the lanthanum.
- U.S. Patent No. 4,107,405 describes electrode materials based on lanthanum and nickel having a formula close to LaNi 5 in which one of the components is partially substituted by a metal selected from those in groups la, II, III, IV and Va of the Periodic Table of elements, and other than lanthanides, in an atomic proportion which is not zero, being higher than 0.1 percent and lower than 25 percent with respect to the lanthanum.
- 4,487,817 describes a negative electrode of electrochemically active material which consists of an intermetallic compound having the formula AB m C n , in which A consists of mischmetal or at least one element selected from Y, Ti, Hf, Zr, Ca, Th, La and the remaining rare earth metals, B consists of two or more elements selected from Ni, Co, Cu, Fe and Mn, and in which C consists of at least one element selected from Al, Cr and Si.
- A consists of mischmetal or at least one element selected from Y, Ti, Hf, Zr, Ca, Th, La and the remaining rare earth metals
- B consists of two or more elements selected from Ni, Co, Cu, Fe and Mn
- C consists of at least one element selected from Al, Cr and Si.
- U.S. Patent No. 4,925,748 describes a hydrogen absorbing alloy represented by the general formula A,.
- A is selected from the group consisting of La, mixtures of La and rare-earth elements, and mischmetal; B is selected from the group Ti, Zr, Ca, Y, Hf and mixtures thereof, C is selected from the group consisting of Ni, Co, Mn, Al, Fe, Cu, Cr and mixtures thereof and D is selected from the group consisting of V, In, TI, Ga and mixtures thereof.
- U.S. Patent No. 4,983,474 describes a hydrogen absorbing Ni-based alloy comprising Ti, Zr, Mn, V, Fe, Al and Ni.
- the patent describes the role of each component in contributing to the properties of the electrochemical cell.
- the patent discusses the role of manganese in improving hydrogen absorption and corrosion resistance in the particular AB,-type system disclosed, and further that the effects of manganese are not fully obtained when its content is below 4% by weight.
- U.S. Patent No. 5,032,475 describes a nickel metal hydride cell having a hydrogen absorbing alloy in the mixture for the negative electrode, represented by the general formula, XY 5 . a Z a ; where X is a rare earth element, Y is Ni and Z is at least an element selected from Co, Mn, Ag, V, Cu and B; namely LaNi 5 (mischmetal) and the like in which Ni is partially replaced by Al, Mn, Fe, Co, Ti, Cu, Zn, Zr, Cr or B.
- U.S. Patent No. 5,034,289 describes the addition of a hydrophobic material to a standard hydrogen absorbing alloy such as MnNi 3 55 Co 0 75 Mn ⁇ ) 4 Al 1() 3 .
- High capacity nickel metal hydride rechargeable cell systems tend to build up heat more rapidly during cycling and dissipate heat more slowly depending on the size of the cells.
- certain sizes of these cells may fall to less than 80% of their rated capacity on repeated charge/discharge cycles when overcharged in excess of 15%, even at room temperature.
- the loss of capacity is believed to result from corrosion or degradation of the AB 5 hydrogen storage alloy comprising the active material in the negative electrode and the electrolyte.
- the corrosion rate is further accelerated by the high operating temperatures and by high temperatures resulting from repeated charge/discharge cycles.
- the pulverization of the active material in the negative electrode resulting from successive charging and discharging of the cell exposes fresh alloy surface to the electrolyte, further adding to the corrosion process.
- the present invention provides hydrogen storage alloy electrodes characterized by using hydrogen storage alloys of a multi-component system containing small amounts of zirconium and/or titanium at levels much lower than those found in prior formulations.
- the levels of these elements have been selected to maintain low hydrogen equilibrium pressure, high capacity, and activation characteristics comparable to prior art hydrogen storage alloys; yet with improved storage characteristics and improved cycle life from reduced corrosion.
- alloys we mean that the elements of the compound are each homogeneously dispersed throughout the metallic matrix.
- the Zr or Ti remains dispersed in the matrix and the formation of ZrNi, and/or TiNi 3 , phases which will not store hydrogen and can raise the operating pressure, is avoided.
- the hydrogen absorbing alloy of the present invention may be represented by the following general formula: LM x Ni A.(B+c+D) Co B Al c Mn D where L is mischmetal with La representing 45% to 70% and the balance being other Rare Earth metals; M is Ti or Zr; X is from 0.001 to 0.01; A is from 4.9 to 5.2 (preferably, 5.0 to 5.1); B is from 0.4 to 1.0; C is from 0.1 to 0.6; and D is from 0 to 0.45.
- an AB 5 -type hydrogen absorbing alloy composition for use in an electrochemical cell is essentially according to the formulation LM Ni A . (B l C+D) Co B Al c Mn D , where L includes mischmetal including between about 45 and 70 percent lanthanum, M is an element selected from the group consisting of titanium and zirconium, X is between 0.001 and 0.01, B and C are each greater than zero, and A is about 5.
- B is between about 0.4 and 1.0
- C is between about 0.1 and 0.6
- D is less than about 0.45.
- X is preferably between about 0.002 and 0.006. more preferably about 0.0035.
- an AB 5 -type hydrogen absorbing alloy composition for use in an electrochemical cell includes between about 0.001 and 0.01 mole percent of an alloying element dispersed throughout the alloy, with the alloying element selected from the group consisting of titanium, zirconium, and combinations thereof.
- the alloy is essentially according to the formulation LM Q 5 , where L represents mischmetal including between about 45 and 70 percent lanthanum, M represents the alloying element, X is between 0.001 and 0.01, and Q includes nickel. In some cases, Q also includes cobalt and aluminum. Manganese is also included in some formulations.
- One preferred formulation is La 063 Ce 026 Nd 008 Pr 003 M x Ni 3 7 Co 078 Al 028 Mn 036 , where M represents an alloying element selected from the group consisting of titanium and zirconium and combinations thereof, and X is between 0.001 and 0.01.
- a method for producing an AB 5 hydrogen storage alloy for use in an electrochemical cell.
- the method includes melting a melt charge in an inert environment under superatmospheric pressure (the melt charge comprising mischmetal, nickel, cobalt and aluminum), adding an alloying element to the molten melt charge (the alloying element selected from the group consisting of zirconium, titanium, and mixtures thereof, the amount of added alloying element selected to produce an alloy having between 0.01 and 0.001 mole percent of the alloying element), and allowing the melt charge to cool to room temperature.
- the melt charge comprising mischmetal, nickel, cobalt and aluminum
- an alloying element selected from the group consisting of zirconium, titanium, and mixtures thereof, the amount of added alloying element selected to produce an alloy having between 0.01 and 0.001 mole percent of the alloying element
- the method of the invention includes providing a melt charge comprising mischmetal, nickel, cobalt and aluminum; placing the melt charge in a furnace; establishing a pressurized furnace environment substantially of argon gas; melting the melt charge while maintaining the furnace environment pressure; adding an alloying element to the molten melt charge, the alloying element selected from the group consisting of zirconium, titanium, and mixtures thereof, the amount of added alloying element selected to produce an alloy with between 0.01 and 0.001 mole percent of said alloying element; and allowing the alloy to cool to less than 50 degrees Celsius.
- the cooled alloy is heat treated for at least about 8 hours at about 1050 degrees Celsius.
- the cooled alloy may be pulverized to produce an alloy powder, which may be sieved to remove particles greater than about 75 microns in size.
- the invention features an electrochemical cell.
- the cell includes a positive electrode containing nickel hydroxide, and a negative electrode containing an AB 5 -type hydrogen absorbing alloy.
- the alloy has between about 0.001 and 0.01 mole percent of an alloying element dispersed throughout the alloy, where the alloying element is selected from the group consisting of titanium, zirconium, and combinations thereof.
- the invention also features, in another aspect, a metallic particle for use in an electrode of an electrochemical cell.
- the particle consists essentially of an AB 5 -type hydrogen absorbing alloy comprising LM Ni A . (B+C l D) Co B Al c Mn D , where L represents mischmetal including between about 45 and 70 percent lanthanum, M represents an alloying element selected from the group consisting of titanium and zirconium and combinations thereof, X is between 0.001 and 0.01, B and C are each greater than zero, and A is about 5.
- the particle will, during use, develop oxides at its surface.
- the mole percentage of the lanthanum should be between about 0.6 and 0.8, and the mole percentage of Ce is preferred to be between about 0.1 and 0.3.
- the remainder of the 1.0 mole percent mischmetal includes Nd and Pr.
- the present invention provides hydrogen storage alloys of the AB 5 -type which contain low levels of zirconium and/or titanium additives, meaning they contain levels of less than 0.01 mole percent zirconium and/or titanium. Conventional AB- 5 type hydrogen storage alloys typically contain levels of 0.01 mole percent or higher.
- the hydrogen storage alloys of the present invention when used in nickel-metal hydride rechargeable batteries, have extended cycle life and high temperature storage time without compromising the alloy's capacity or hydrogen equilibrium pressure.
- Fig. 1 illustrates a wound electrochemical cell.
- Figs. 2-5 show hydrogen desorption characteristics of alloys with and without Zr and Ti.
- Figs. 6-11 show cycle life at room and elevated temperatures for alloys with various amounts of Zr and Ti.
- Figs. 12 and 13 show the increase in the storage life of a cell resulting from the addition of Zr 0005 to two alloys.
- Fig. 14 illustrates an effect of higher levels of Zr.
- Figure 1 shows a typical rechargeable cell which consists of a Ni-plated steel can 4, a safety vent 6, a sealing plate 7, a metal hydride negative electrode 1, a nickel positive electrode 2, a positive electrode cap 5. a separator 3, an insulating gasket 8, and a positive electrode collector 9.
- the positive electrode is made by mixing spherical nickel hydroxide and cobalt monoxide powders, at a weight ratio of 92.6:7.4, with a binding medium in the presence of water to produce a paste, which may be applied to a highly porous felt or foam substrate.
- the hydrogen absorbing alloy negative electrode is made by forming a layer of a mixture of hydrogen absorbing powder and carbon at a weight ratio of 1000:7 with a binding medium and water to produce a paste, which may be applied to a conductive core substrate, typically nickel foil.
- Paste formulations are described in more detail in pending U.S. Patent Application No. 08/884,592, the contents of which are hereby incorporated by reference. Preparation of the Alloys
- the hydrogen absorbing alloy is prepared using the following general procedure.
- the Ce-mischmetal approximately composition La: 25%, Nd: 175%, Pr: 6%, Ce: balance
- La-mischmetal approximately-mischmetal (approximate composition Nd: 10%, Pr: 2.5%, Ce: 1%, La: balance)
- nickel, cobalt, aluminum, lanthanum, neodymium, and praseodymium are melted together in the required quantities to achieve the desired compositions.
- the melt charge is loaded into a magnesia crucible installed in an induction furnace. The atmosphere inside the furnace is evacuated to obtain a vacuum state of 0.02 torr.
- the furnace is filled with argon to a pressure of 780 to 790 torr which is maintained during the melting operation.
- Zirconium and/or titanium are added to the molten charge several minutes before it is poured on to a copper block and allowed to cool to ambient temperature (less than 50 degrees C).
- ambient temperature less than 50 degrees C.
- the Zr/Ti is dispersed throughout the matrix of the alloy. Titanium is a bit harder to dissolve than zirconium, and tends to come out in an undesirable secondary phase with nickel (TiNi 3 ).
- the resulting alloy is heat treated for 6 to 12 hours (preferably about 8 hours or more) at 950 to 1150 C (preferably about 1050 C) in argon to homogenize the casting and to give the pressure plateau of the alloy more definition.
- the heat treated alloy is then pulverized by repeated hydrogen absorption and desorption. Other pulverization means, such as mechanical milling or jet milling, can also be used.
- the resulting powder is sieved to remove particles greater than 75 microns.
- K La 045 Ce 035 Nd 0 , 5 Pr 005 Zr 00034 N ⁇ 365 Co 075 A1 055 Mn 00
- L La 053 Ce 003 Nd 034 Pr 0 ,Ni 408 Co 04 Al 034 Mn 04
- Figures 2 and 3 show the addition of 0.15% by weight of Zr (Zr 0007 ) or Ti (Ti 0013 ) to an alloy of La 045 Ce 035 Nd 015 Pr 005 Ni 37 Co 07 Al 06 has no detrimental effects on its desorption pressure or capacity.
- metal hydride alloys are desired to have hydrogen equilibrium plateau pressures at 45° from 0.2 to 2 bars and capacity of at least 260 mAhr/g in the region between 0.05 and 2 bars. With a plateau pressure of less than about 0.2 bar, the alloy has less of a tendency to give up charge, while alloys with plateau pressures of greater than about 2 bars may lead to excessive internal cell pressure.
- Figure 4 shows the addition of 0.13% Zr by weight (Zr 0006 ) to an alloy of La 065 Ce 02 Nd 0 ,Pr 005 Ni 365 Co 085 Al 05 has no significant effect on its desorption pressure or capacity.
- Figure 5 shows the addition of 0.15% Zr by weight (Zr 0 ⁇ 07 ) to an alloy of La 03 Ce 05 Nd 015 Pr 005 Ni 35 Co 075 Mn 043 Al 032 results in a slight increase in its desorption pressure and a slight decrease in its desorption capacity.
- Figures 6 through 11 show the improvement in various charge- discharge (cycling) conditions for several alloy formulations with and without Zr or Ti additions. Each figure shows an increase in the number of cycles to the 80% cut-off as a result of the addition of Ti or Zr.
- Figures 12 and 13 show the increase in the time for a discharged cell at 80°C to fall to an open circuit voltage of 1.0 volt resulting from the addition of Zr 0005 to an alloy of La 0 7 Ce 0 , 5 Nd 0 ] Pr 005 Ni 3 7 Co 0 85 Al 045 and to an alloy of La 063 Ce 0 26 Nd 008 Pr 003 Ni 3 68 Co 0 78 Mn 0 36 Al 028 .
- the time needed for the cell voltage to drop to 1.0 volt indicates the useful storage life of the cell.
- Figure 14 shows the disadvantage of higher Zr amounts used in prior art.
- Zr 0 has been added as to Alloy F
- Alloy T (La 0 45 Ce 035 Nd 0
- the resulting alloy is characterized by higher plateau pressure than Alloy D (with Zr 0 007 ) and significantly lower capacity, approximately 50 mAhr/g or 18% in the region between 0.05 bars and 2 bars.
- the plateau pressure of Alloy T remains in the useful range, Alloy T's capacity is too low to be useful in commercial Nickel-rechargeable cells.
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP52793998A JP2002516023A (en) | 1996-12-19 | 1997-12-16 | AB5 type hydrogen storage alloy for use in rechargeable electrochemical cells and method for producing the same |
EP97953269A EP0953216A1 (en) | 1996-12-19 | 1997-12-16 | Hydrogen storage alloys of the ab 5? type for use in rechargeable electrochemical cells, and methods of producing them |
AU57052/98A AU5705298A (en) | 1996-12-19 | 1997-12-16 | Hydrogen storage alloys of the ab5 type for use in rechargeable electrochemical cells, and methods of producing them |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US3361696P | 1996-12-19 | 1996-12-19 | |
US60/033,616 | 1996-12-19 |
Publications (1)
Publication Number | Publication Date |
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WO1998027604A1 true WO1998027604A1 (en) | 1998-06-25 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1997/023271 WO1998027604A1 (en) | 1996-12-19 | 1997-12-16 | Hydrogen storage alloys of the ab5 type for use in rechargeable electrochemical cells, and methods of producing them |
Country Status (7)
Country | Link |
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US (1) | US6074783A (en) |
EP (1) | EP0953216A1 (en) |
JP (1) | JP2002516023A (en) |
AU (1) | AU5705298A (en) |
TW (1) | TW363288B (en) |
WO (1) | WO1998027604A1 (en) |
ZA (1) | ZA9711221B (en) |
Families Citing this family (1)
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DK177652B1 (en) * | 2012-07-10 | 2014-02-03 | Pr Electronics As | Converter with shared current path and isolation barrier |
Citations (7)
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JPH03274241A (en) * | 1990-03-24 | 1991-12-05 | Japan Storage Battery Co Ltd | Hydrogen occluding electrode |
JPH03274240A (en) * | 1990-03-24 | 1991-12-05 | Japan Storage Battery Co Ltd | Hydrogen occluding electrode |
JPH03294444A (en) * | 1990-04-11 | 1991-12-25 | Agency Of Ind Science & Technol | Hydrogen occluding electrode |
CN1065353A (en) * | 1992-04-25 | 1992-10-14 | 冶金工业部钢铁研究总院 | The hydrogen-storage alloy that is used for secondary battery negative pole |
JPH06279900A (en) * | 1993-03-23 | 1994-10-04 | Shin Etsu Chem Co Ltd | Hydrogen storage alloy and electrode using the alloy |
US5376474A (en) * | 1993-02-05 | 1994-12-27 | Sanyo Electric Co., Ltd. | Hydrogen-absorbing alloy for a negative electrode and manufacturing method therefor |
JPH07147161A (en) * | 1993-11-25 | 1995-06-06 | Toshiba Battery Co Ltd | Metal oxide-hydrogen secondary battery |
Family Cites Families (9)
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US4605603A (en) * | 1983-12-26 | 1986-08-12 | Kabushiki Kaisha Toshiba | Hermetically sealed metallic oxide-hydrogen battery using hydrogen storage alloy |
US4696873A (en) * | 1985-06-21 | 1987-09-29 | Kabushiki Kaisha Toshiba | Rechargeable electrochemical cell with a negative electrode comprising a hydrogen absorbing alloy including rare earth component |
EP0284333B1 (en) * | 1987-03-25 | 1995-11-29 | Matsushita Electric Industrial Co., Ltd. | Sealed type nickel-hydride battery and production process thereof |
US4898794A (en) * | 1988-12-27 | 1990-02-06 | Mitsubishi Metal Corporation | Hydrogen absorbing Ni,Zr-based alloy and rechargeable alkaline battery |
FR2670609B1 (en) * | 1990-12-13 | 1995-07-07 | Sorapec | NICKEL POSITIVE ELECTRODE. |
DE69219000T2 (en) * | 1991-05-10 | 1997-07-24 | Japan Storage Battery Co Ltd | Prismatic gas-tight alkaline battery with a nickel hydroxide electrode |
JPH0688798B2 (en) * | 1991-11-07 | 1994-11-09 | 株式会社ガラス調合センター | Method for melting glass using packaging container made of organic material |
CN1029809C (en) * | 1991-12-28 | 1995-09-20 | 南开大学 | Hydrogen-bearing alloy electrode |
DE69317967T2 (en) * | 1992-09-14 | 1998-12-10 | Kabushiki Kaisha Toshiba, Kawasaki, Kanagawa | Hydrogen-absorbing alloy for batteries, process for their production and nickel-metal hydride secondary battery |
-
1997
- 1997-12-04 US US08/978,699 patent/US6074783A/en not_active Expired - Lifetime
- 1997-12-12 ZA ZA9711221A patent/ZA9711221B/en unknown
- 1997-12-16 EP EP97953269A patent/EP0953216A1/en not_active Withdrawn
- 1997-12-16 AU AU57052/98A patent/AU5705298A/en not_active Abandoned
- 1997-12-16 WO PCT/US1997/023271 patent/WO1998027604A1/en not_active Application Discontinuation
- 1997-12-16 JP JP52793998A patent/JP2002516023A/en active Pending
- 1997-12-19 TW TW086119329A patent/TW363288B/en active
Patent Citations (7)
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JPH03274241A (en) * | 1990-03-24 | 1991-12-05 | Japan Storage Battery Co Ltd | Hydrogen occluding electrode |
JPH03274240A (en) * | 1990-03-24 | 1991-12-05 | Japan Storage Battery Co Ltd | Hydrogen occluding electrode |
JPH03294444A (en) * | 1990-04-11 | 1991-12-25 | Agency Of Ind Science & Technol | Hydrogen occluding electrode |
CN1065353A (en) * | 1992-04-25 | 1992-10-14 | 冶金工业部钢铁研究总院 | The hydrogen-storage alloy that is used for secondary battery negative pole |
US5376474A (en) * | 1993-02-05 | 1994-12-27 | Sanyo Electric Co., Ltd. | Hydrogen-absorbing alloy for a negative electrode and manufacturing method therefor |
JPH06279900A (en) * | 1993-03-23 | 1994-10-04 | Shin Etsu Chem Co Ltd | Hydrogen storage alloy and electrode using the alloy |
JPH07147161A (en) * | 1993-11-25 | 1995-06-06 | Toshiba Battery Co Ltd | Metal oxide-hydrogen secondary battery |
Non-Patent Citations (4)
Title |
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PATENT ABSTRACTS OF JAPAN vol. 016, no. 086 (C - 0916) 3 March 1992 (1992-03-03) * |
PATENT ABSTRACTS OF JAPAN vol. 016, no. 128 (C - 0924) 2 April 1992 (1992-04-02) * |
PATENT ABSTRACTS OF JAPAN vol. 095, no. 001 28 February 1995 (1995-02-28) * |
PATENT ABSTRACTS OF JAPAN vol. 095, no. 009 31 October 1995 (1995-10-31) * |
Also Published As
Publication number | Publication date |
---|---|
AU5705298A (en) | 1998-07-15 |
EP0953216A1 (en) | 1999-11-03 |
ZA9711221B (en) | 1998-06-23 |
US6074783A (en) | 2000-06-13 |
JP2002516023A (en) | 2002-05-28 |
TW363288B (en) | 1999-07-01 |
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